Our invention relates to mixtures of one or more t-mercapto terpene isomers defined according to the structure: ##STR3## wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond taken further together with .alpha.-terpineol, .beta.-phenylethyl alcohol, 3-methyl-1-phenyl-pentanol-5 and/or butanoyl cyclohexane derivatives as well as organoleptic uses thereof and processes for preparing such mixtures including the novel process of reacting the epoxide defined according to the structure: ##STR4## with an alkali metal thiocyanate in order to form the compound having the structure: ##STR5## and then reducing the compound having the structure: ##STR6## with lithium aluminum hydride followed by treatment with aqueous mineral acid to form a compound having the structure: ##STR7##
Chemical compounds which can provide natural rose petal, green, iris and hyacinth aroma profiles are highly desirable in the art of perfumery. Many of the natural materials which provide such fragrances and contribute such desired nuances to perfumery compositions are high in cost, unobtainable at times, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
By the same token, materials which can provide guava-like, grapefruit-like, black current-like, tomato leaf and passion fruit aroma and taste nuances are highly desirable in the art of application of flavors to foodstuffs, toothpastes, chewing gums, medicinal products and chewing tobaccos. Many of the natural materials which provide such flavor nuances are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products. Such flavor nuances, furthermore, are highly useful in flavoring tobacco, guava, grapefruit, tropical fruit, raspberry, strawberry and passion fruit-flavored foodstuffs.
Artificial flavoring agents for foodstuffs have received increasing attention in recent years. For many years such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in quality, type and treatment of the raw materials. Such variations can be reflected in the end product and result in unfavorable flavor characteristics in said end product. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increased tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies and dairy dessert products and the like are apt to be stored prior to use.
The fundamental problem in creating artificial flavor agents is that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods, medicinal products, chewing gums, toothpastes and chewing tobaccos is not completely known. This is noticeable in products having tomato, guava, grapefruit, tropical fruit-like, raspberry, strawberry and passion fruit flavor characteristics.
Even more desirable are products that can serve to substitute for difficult to obtain natural perfumery oils and at the same time substitute for natural flavoring ingredients in foodstuffs, chewing gums, medicinal products, toothpastes and chewing tobaccos.
The compound having the structure: ##STR8## is a known ingredient in grapefruit aroma and taste. The compound having the structure: ##STR9## occurs naturally in grapefruit aromas as disclosed by Demole, Enggist and Ohloff, Helvetica Chimica Acta, Vol. 65, Fasc. 6, (1982), Number 176 at page 1784 (title: 1-p-Menthene-8-thiol:A Powerful Flavor Impact Constituent of Grapefruit Juice (Citrus paradisi MacFayden)).
The compound having the structure: ##STR10## as well as its individual isomers having the structures: ##STR11## is also disclosed and claimed for its use in augmenting or enhancing the aroma or taste of grapefruit flavored foodstuffs in published European patent application No. 54,847 published on June 30, 1982 relying on a priority date of Dec. 23, 1980 (Swiss patent application No. 9513/80) assigned to Firmenich S. A. of Geneva, Switzerland. The said published European application No. 54,847 also discloses and claims the use of the compounds having the structures: ##STR12## in augmenting or enhancing the aroma of perfume compositions and perfumed articles.
Nothing in published European patent application No. 54,847 discloses the unexpected, unobvious and advantageous results when using mixtures of such t-mercapto terpenes as those having the structures: ##STR13## in admixture with .alpha.-terpineol having the structure: ##STR14## .beta.-phenylethyl alcohol, 3-methyl-1-phenyl-pentanol-5 and/or butanoyl cyclohexane derivatives defined according to the generic structure: wherein the dashed lines are as defined above.
The individual components of our novel mixture are known in the art of perfumery and a number of them are also known individually in augmenting or enhancing the aroma or taste of foodstuffs, chewing gums, toothpastes and medicinal products.
Thus, .beta.-phenylethyl alcohol defined according to the structure: ##STR15## is indicated by Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)" published 1969, Volume II at Monograph 2513 to have a mild and warm, rose, honey-like odor of moderate to poor tenacity. Arctander further indicates that phenylethyl alcohol in its poorer grades shows earthy, pungent, more hyacinth-like topnotes or greener "gassy" notes. At Monograph 2513, Arctander also indicates that .beta.-phenylethyl alcohol finds some use in flavor compositions, mainly in imitation butter, strawberry, raspberry ("very common ingredient"), caramel, honey, melon and in various fruit complexes. Arctander indicates that the concentration of phenylethyl alcohol used is from about 0.1 up to about 20 ppm.
The compound having the structure: ##STR16## is indicated to be useful in perfumery in published German Offenlegungsschrift No. 26 15 393 published on Oct. 21, 1976. The German Offenlegungsschrift corresponds to U.S. Pat. No. 4,067,910 issued on Jan. 10, 1978. Such compounds are also indicated to be useful for augmenting or enhancing the aroma or taste of foodstuffs.
U.S. Pat. No. 4,217,253 issued on Aug. 12, 1980 discloses mixtures of 3-methyl-1-phenyl-pentanol-5 having the structure: ##STR17## and one or more butanoyl cyclohexane derivatives defined according to the structure: ##STR18## wherein one of the dashed lines is a carbon-carbon double bond or two of the dashed lines are carbon-carbon double bonds but that when two of the dashed lines each represents a carbon-carbon double bond, then the carbon-carbon double bonds are conjugated. Examples of the butanoyl cyclohexane derivatives of U.S. Pat. No. 4,217,253 are those having the structure: ##STR19## (wherein the dashed line in the structure: ##STR20## represents a configuration of the butanoyl moiety "trans" with respect to the methyl moiety at the "2" position on the cyclohexene ring). It is disclosed in said U.S. Pat. No. 4,217,253 that perfume compositions and perfumes having extended long-lasting, highly intense and natural-like rosey notes and perfumed articles having extended, long-lasting, highly intense rosey aromas with woody, green and earthy notes may be provided by the utilization of mixtures of (i) one or more butanoyl cyclohexane derivatives defined according to the structure: ##STR21## wherein one or two of the dashed lines is a carbon-carbon double bond and the other of dashed lines are carbon-carbon single bonds with the proviso that if two of the dashed lines are carbon-carbon double bonds, the carbon-carbon double bonds are conjugated and (ii) 3-methyl-1-phenyl-pentanol-5 racemic mixtures or individual stereoisomers having one of the structures: ##STR22## In U.S. Pat. No. 4,217,253 it is indicated that organoleptic properties obtained when using the combination of mixtures of 3-methyl-1-phenyl-pentanol-5 and one or more butanoyl cyclohexane derivatives as defined supra is more than merely additive of the individual organoleptic properties of the 3-methyl-1-phenyl-pentanol-5 compound taken alone or in combination and the butanoyl cyclohexane derivatives (taken alone or in combination with one another) and that the effect is synergistic. The synergism existent as a result of practicing our invention, however, is unexpected, unobvious and advantageous notwithstanding the synergism described and taught in U.S. Pat. No. 4,217,253.
U.S. Pat. No. 4,028,279 entitled "Novel Fragrance Compositions Containing 2,6,6-Trimethyl-1-Cyclohexene-1-yl Acetaldehyde and Phenyl C.sub.6 Ketone" relates to mixtures of (i) either of both of the phenyl C.sub.6 ketones, 2,5-dimethyl-5-phenylhexanone-4 and 2,5-dimethyl-5-phenylhexen-1-one and (ii) 2,2,6-trimethyl-1-cyclohexen-1-yl acetaldehyde used to alter, modify, enhance or impart aromas in or to perfumes, perfume compositions and/or perfumed articles. It is disclosed in said U.S. Pat. No. 4,028,279 that such perfume compositions containing such mixtures have intense rosey aromas with woody, green and earthy notes. The structure of the phenyl C.sub.6 ketones disclosed in U.S. Pat. No. 4,028,279 is: ##STR23## The structure of the betacyclohomocitral used in U.S. Pat. No. 4,028,279 is: ##STR24## wherein the dashed line may be either a carbon-carbon single bond or a carbon-carbon double bond.
In U.S. Pat. No. 3,595,508 issued on May 25, 1976, mixtures of (i) 2,2,6-trimethyl-1-cyclohexen-1-yl acetaldehyde and (ii) 2,6,6-trimethyl crotonyl-1,3-cyclohexadiene having the structure: ##STR25## are indicated to produce in perfumes, rosey, woody, camphoraceous, green and earthy notes.
Nothing in the prior art teachings imply or state that such mixtures as are disclosed and claimed in the instant case can be used to enhance and extend specific rose nuances of such materials as .beta.-phenylethyl alcohol, .alpha.-terpineol, butanoyl cyclohexane derivatives having the generic structure: ##STR26## and 3-methyl-1-phenyl-pentanol-5 using one or both of the t-mercapto terpene derivatives defined according to the structures: ##STR27## wherein one of the dashed lines is a carbon-carbon double bond and the other of the dashed lines is a carbon-carbon single bond.